Transcript Esters

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PART 2
1
Absorption range /
cm-1
Bonds responsible
Examples
4000-2500
2500-2000
2000-1500
Below 1500
Single bonds to H
Triple bonds
Double bonds
various
O-H, C-H, N-H
C≡C, C≡N
C=C, C=O
C-O, C-X
 Below 1500cm-1 the IR spectrum can be quite
complex
 This region is characteristic of a particular
molecule
 Hence known as ‘fingerprint region’
2
Principles and practice
4
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In the infrared region of the spectrum photons
do not excite electrons but may induce
vibrational excitation of covalently bonded
atoms and groups.
Molecules experience a wide variety of
vibrational motion.
Virtually all organic compound will absorb
radiation that corresponds to these vibrations.
6
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KBr pellet
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Salt cells:
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Good for powders; a few milligrams of the sample power and
an excess of KBr are finely ground and pressed under high
pressure into a pellet. This is a useful and very general method
for solids.
Good for organic liquids; the liquid is placed into a reservoir
milled in alkali salt windows.
Nujol mull:

The material of interest is suspended in oil, such as mineral oil,
and the resulting paste is spread thinly on a salt window to
form a film. This is a good technique for oils and waxy solids
that do not press well into pellets.
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Infrared spectra may be obtained from samples
in all phases (liquid, solid and gaseous).
Liquids are usually examined as a thin film
sandwiched between two polished salt plates
(note that glass absorbs infrared radiation,
whereas NaCl is transparent).
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If solvents are used to dissolve solids, care must be
taken to avoid obscuring important spectral
regions by solvent absorption. Perchlorinated
solvents such as carbon tetrachloride, chloroform
and tetrachloroethene are commonly used.
Alternatively, solids may either be incorporated in
a thin KBr disk, prepared under high pressure, or
mixed with a little non-volatile liquid and ground
to a paste (or mull) that is smeared between salt
plates.
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Water has a dipole moment and absorbs light
in the infrared very strongly.
It is difficult to measure the infrared spectrum
of biological materials in water due to the
spectrum of water obscuring the information.
A combination of H2O and D2O is often used to
overcome this problem.
11
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A molecule composed of n-atoms has 3n
degrees of freedom, six of which are
translations and rotations of the molecule itself.
This leaves 3n-6 degrees of vibrational freedom
(3n-5 if the molecule is linear).
Vibrational modes are often given descriptive
names, such as stretching, bending, scissoring,
rocking and twisting.
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Vibrational modes are often given
descriptive names, such as stretching,
bending, scissoring, rocking, waging and
twisting.
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The four-atom molecule of formaldehyde, the
gas phase spectrum of which is shown,
provides an example of these terms.
We expect six fundamental vibrations (12
minus 6), and these have been assigned to the
spectrum absorptions.
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The exact frequency at which a given vibration occurs
is determined by the strengths of the bonds involved
and the mass of the component atoms.
In practice, infrared spectra do not normally display
separate absorption signals for each of the 3n-6
fundamental vibrational modes of a molecule.
The number of observed absorptions may be increased
by additive and subtractive interactions leading to
combination tones and overtones of the fundamental
vibrations, in much the same way that sound
vibrations from a musical instrument interact.
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The number of observed absorptions may be decreased
by molecular symmetry, spectrometer limitations, and
spectroscopic selection rules.
One selection rule that influences the intensity of
infrared absorptions, is that a change in dipole moment
should occur for a vibration to absorb infrared energy.
Absorption bands associated with C=O bond stretching
are usually very strong because a large change in the
dipole takes place in that mode.
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
Stretching frequencies are higher than
corresponding bending frequencies. (It is easier to
bend a bond than to stretch or compress it.)
Bonds to hydrogen have higher stretching
frequencies than those to heavier atoms.
Triple bonds have higher stretching frequencies
than corresponding double bonds, which in turn
have higher frequencies than single bonds.
(Except for bonds to hydrogen).
Infrared group frequencies
(correlation chart)
Infrared group frequencies
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Alcohols and amines display strong broad O-H and NH stretching bands in the region 3400-3100 cm-1. The
bands are broadened due to hydrogen bonding and a
sharp 'non-bonded' peak can often be seen at around
3400 cm-1.
Alkene and alkyne C-H bonds display sharp stretching
absorptions in the region 3100-3000 cm-1. The bands are
of medium intensity and are often obscured by other
absorbances in the region (i.e., OH).

Triple bond stretching absorptions occur in the
region 2400-2200 cm-1. Absorptions from nitriles
are generally of medium intensity and are
clearly defined. Alkynes absorb weakly in this
region unless they are highly asymmetric;
symmetrical alkynes do not show absorption
bands.
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Carbonyl stretching bands occur in the region
1800-1700 cm-1. The bands are generally very
strong and broad. Carbonyl compounds which
are more reactive in nucleophilic addition
reactions (acyl halides, esters) are generally at
higher wave number than simple ketones and
aldehydes, and amides are the lowest,
absorbing in the region 1700-1650 cm-1.

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Carbon-carbon double bond stretching occurs in
the region around 1650-1600 cm-1. The bands are
generally sharp and of medium intensity.
Aromatic compounds will typically display a
series of sharp bands in this region.
Carbon-oxygen single bonds display stretching
bands in the region 1200-1100 cm-1. The bands
are generally strong and broad. You should note
that many other functional groups have bands
in this region which appear similar.
Examples of infrared spectra
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The infrared spectrum of benzyl alcohol displays
a broad, hydrogen-bonded -OH stretching band
in the region ~3400 cm-1, a sharp unsaturated
(sp2) CH stretch at about 3010 cm-1 and a
saturated (sp3) CH stretch at about 2900 cm-1;
these bands are typical for alcohols and for
aromatic compounds containing some saturated
carbon.
Acetylene (ethyne) displays a typical terminal
alkyne C-H stretch.
Examples of infrared spectra

Saturated and unsaturated CH bands are
shown clearly in the spectrum of vinyl acetate
(ethenyl ethanoate). This compound also shows
a typical ester carbonyl at 1700 cm-1 and an
example of a carbon-carbon double bond
stretch at about 1500 cm-1. Both of these bands
are shifted to slightly lower wave numbers
than are typically observed (by about 50 cm-1)
by conjugation involving the vinyl ester group.
1-Buthanol

n-Butanol CH3CH2CH2CH2OH

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O-H Stretch 3330 cm-1
C-O Stretch 1070 cm-1
Hydrogen Bonded
(Ethanoic acid)
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Ethanoic Acid CH3COOH
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O-H Stretch 3050 cm-1
C=O stretch 1715 cm-1
C-O Stretch 1295 cm-1
Hydrogen Bonded
(2-butanone)

2-Butanone CH3COCH2CH3

C=O Stretch 1715 cm-1
(ethyl ethanoate)

Ethyl Ethanoate CH3COOC2H5
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C=O Stretch 1710 cm-1
C-O Stretch 1240 cm-1
C-O Stretch 1050 cm-1
43
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Step 1
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Look first for the carbonyl C=O band.
Look for a strong band at 1820-1660 cm-1. This band is
usually the most intense absorption band in a
spectrum. It will have a medium width. If you see the
carbonyl band, look for other bands associated with
functional groups that contain the carbonyl by going to
step 2.
If no C=O band is present, check for alcohols and go to
step 3.
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Step 2
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If a C=O is present you want to determine if it is part
of an acid, an ester, or an aldehyde or ketone. At this
time you may not be able to distinguish aldehyde
from ketone.
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ACID
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Look for indications that an O-H is also present. It has
a broad absorption near 3300-2500 cm-1. This actually
will overlap the C-H stretch. There will also be a C-O
single bond band near 1100-1300 cm-1. Look for the
carbonyl band near 1725-1700 cm-1.
ESTER

Look for C-O absorption of medium intensity near
1300-1000 cm-1. There will be no O-H band.
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ALDEHYDE
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Look for aldehyde type C-H absorption bands. These
are two weak absorptions to the right of the C-H
stretch near 2850 cm-1 and 2750 cm-1 and are caused
by the C-H bond that is part of the CHO aldehyde
functional group. Look for the carbonyl band around
1740-1720 cm-1.
KETONE

The weak aldehyde CH absorption bands will be
absent. Look for the carbonyl CO band around 17251705 cm-1.
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Step 3
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If no carbonyl band appears in the spectrum, look
for an alcohol O-H band.
ALCOHOL
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Look for the broad OH band near 3600-3300 cm-1 and
a C-O absorption band near 1300-1000 cm-1.
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Step 4
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ALKENE
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If no carbonyl bands and no O-H bands are in the spectrum,
check for double bonds, C=C, from an aromatic or an alkene.
Look for weak absorption near 1650 cm-1 for a double bond.
There will be a CH stretch band near 3000 cm-1.
AROMATIC

Look for the benzene, C=C, double bonds which appear as
medium to strong absorptions in the region 1650-1450 cm-1. The
CH stretch band is much weaker than in alkenes.
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Step 5
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If none of the previous groups can be identified,
you may have an alkane.
ALKANE
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The main absorption will be the C-H stretch near
3000 cm-1. The spectrum will be simple with another
band near 1450 cm-1.
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Step 6
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If the spectrum still cannot be assigned you may
have an alkyl halide.
ALKYL BROMIDE
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Look for the C-H stretch and a relatively simple
spectrum with an absorption to the right of 667 cm-1.